Process for coloring and waterproofing textile material



go of this a uniform coloring takes place.

Patented June 28, 11938 strap stares gram" @KQQEQE PRQCESS FOR GOILGRHNG AND WATER- ?RQQlE-ENG TEXTILE MAUI-HERBAL No Drawing. Application December 13, 1933, Se-

rial No. 702,259. In Germany December .15,

2 Claims.

This invention relates to a process for simultaneously coloring and water-proofing textile materials in one bath. It has been found that the application of the dispersed water-proofing substances can be effected simultaneously with the coloring matter. The surprising discovery has been made that coloring matter or dyestufi and dispersed water-repelling particles do not impair each others action in any operative M phase, and that therefore, in spite of the presence of an emulsion, the coloring or dyeing takes place uniformly and. not, as might be expected, irregularly, whereas for example uncleaned or unscoured cotton fibre containing a small quane 15 city of wax, and readily repelling water, colors very irregularly, and in addition it is known that the parts of fibres coated with paraiiin are not colored at all.

The surprising technical effect is that in spite The process represents a very economical simplification of textile finishing since the operative time is considerably shortened, one operation being avoided. Thus the cost in manufacture is 25 reduced considerably. After the dyeing it is not necessary to dry, before impregnating and then to dry again. The water-proofing emulsions are simply added to the coloring bath and the dyeing is efiected in the usual way. The resulting 3o wares are uniformly dyed and rep'el water to remarkable extent. The impregnation produced in this way will stand rinsing even in the case of moist articles, so that the auxiliary chemicals can be removed and in this manner subse-- ga quent damage to the fibre is avoided.

g All emulsions used for water-proofing purposes may be employed, consisting of aqueous emulsions of water-proofing substances like parafiin, aluminium soaps, and so forth, or mix-- as tures of such substances.

The following special emulsions also belong to emulsions of this type:

(1) Aqueous emulsions of soaps of 'polyvalent 5 metals ostween further subdivi sions of these'emulsions, which relate to the pro duction; they are subdivided into v (0.) those homogenizedunde'r pressure.

lb) those emulsified in stirring machines, emulsifying machines or colloid mills.

14 parts of oil soap are stirred up with 15 parts of swollen bone glue and then diluted with water. This solution is stirred into 500 parts of a solution of formate of alumina having a specific gravity of 1.095. Thereupon 1-2% of hexaline, butanol, acetic ester, acetone and the like are added. This emulsion is homogenized by forcing through ducts by means of suitable machines at a pressure of 60 atmospheres pressure.

(2) Emulsions according to (1 both as regards composition and production, but characterized by the addition of water-proofing substances Water-proofing substances like paraffins, waxes, resins, fats, fatty oils or mineral oils may 2@ be ,used. Here also a distinction is to be drawn between emulsions which are (a) homogenized under pressure and (1)) stated briefly, emulsified.

By saponifying a mixture of 3.10 kg. of fatty acid with 4 kg. of mineral oil and 7.4 kg. of paraflln an emulsion is produced to which are added 1.29 kg. of high class glue dissolved in water. This substance is mixed with anialuminium formate solution which has been prepared by dlssolving 1.55 kg. of hydroxide of alumina in 1.75 kg. of formic acid. The whole is then homogenized at atmospherespressure. At the concentration employed 50 kg. of a' white paste are then obtained after cooling, a 2.5% solution of which is sufficient for impregnation purposes.

(3) Emulsions of water-moofing' substances which contain water-soluble salts of polytalent metals, chiefly wcter-soluble aluminium 40 salts, with a positive disperse phase All the above mentioned three groups of emulsions are acidic, and their disperse'phase is positively charged. They all stabilize by means of colloids which swell inwaterfmost advanta- 5 .geously however by means'of glue and gelatin.

(4) Emulsions having a negative dispersed part consisting of soap, glue, gelatin, starch, dextrin, aliphatic or aromatic sulphonic acids as emulsifying agent The disperse phase consists of the waterproofing substances already mentioned above.

5 parts of glue are dissolved in 100 parts of water and to this solution are added 4 parts of the sodium salt of amylnaphthalene sulphonic acid. Into this emulsifying solution is stirred a "mixture of 22 parts of paraffin, 4 parts of cetyl alcohol and 6 parts of olive oil. The whole is worked up in a colloid mill to a fine emulsion.

The process may be carried out by adding the waterproofing substance as such to the dye bath, for example in the case of substantive dyes or acid .wool dyes. Thewater-proofing substance, however,-may also be added to the individual treatment baths in the dyeing, for example to the copper bath, to the after-chroming bath, to the generating bath of naphtol dyes, to the vat or to the aluminous mordant. In the latter case those emulsions are advantageously preferred which already contain aluminium salts. Such emulsions occur in commerce in gelatinous form and consist of aqueous aluminium formate solutionas continuous phase, paramn or paraffin-like substance as the disperse phase, and glue as stabilizing and gelatinizing agent. The following manufacturing receipt will illustrate the composition of paraffin oil are stirred in. Whilst continuously Y stirring in the hot, parts of aluminium formate dissolved in 400 parts of water are slowly various substances compounded together in varying amounts. The use as well of the oils which are usual in dyeing operations, which consist of sulphonated fatty acids or aromatic substances, and which are used for wetting or equalizingpurposes, does not impair the action of the impregnation.

Example 1.Substantive dyeing Makko fabric is treated with the following bath: Ten grams of a-gelatinized emulsion are dispersed in 500 grams of a 1% tartaric acid solution. The emulsion used has the following composition:

80 parts of gelatin are dissolved in 1000 parts of water and a. mixture of 40 parts of cake paramn Water a 1200 An emulsion as in Example 1 and 40 parts of paraflin oil are emulsified therein. This emulsion is treated with formate of alumina of 7 B. I The diluted emulsion solution is poured into a bath of the following composition:

Parts 5 Water 1 500 Diamine black BH, (Schultz Farbstofltabellen 7th edition, volume 1, No. 393) 2 Glaubers salt g 15 Calcined soda 15 10 The cotton fabric is introduced in this solution at 60 C. and, whilst thoroughly stirring, the whole brought to boiling, maintained at the boiling Reduction in height in the examination of the cotton cms". 30 Drop sequence drops in 7 seconds 10 Drop weight mg The following drop values are obtained:

I Drops Cotton dyed without water-proofing agent in the dye bath 2 30 Material impregnated in the usual way with the Waterproofing substance as previously described diluted 1:100, i. e. as 10 g./litre, impregnated 10 min. at 60 C 1d Dyed and impregnated as described above in Example 1 -31 It follows from this that the water-proof quality when waterproofing in the dye bath is considerably higher than is produced byimpregnating in the usual way.

In order to examine the fastness to rinsing and to prove that the impregnating substance adheres very firmly, the piece impregnated in the dye bath is to be, boiled in pure water for 3 minutes and then dried. The imperviousness to water still amounted to 10 drops after this treatment.

Example 2.--Chroming dyestufi Cotton fabric is dyed in the following bath:

Grams Dianil chrome brown R (Schultz Farbstofitabellen 7th edition, volume 1, No. 682) 2 Calcined soda 10 Glaubers salt 15 Tartaric acid 4 The imperviousness to water amounts under the same conditions as in Example 1 to 3 drops, after-chromed at 60 C. for half an hour,-Drop value: 2 drops.

A parallel experiment has been then carried out in which 10 parts of the same gelatinous emulsion as in Example 1 were added to 1000 parts of bath, after which dyeing was effected at 60 C.

for half an hour, and "the material rinsed, squeezed out and ironed-Drop value: 19 drops.

After-chroming was then carried out in the following bath:

7 Parts Water 1150 .7 Copper sulphate- 2. 5 Potassium dichromate r i 2.5 Glacial acetic acid 5 10 Drop value: 25 drops.

- delay fixed during half Example 3.--;Basic dyestufis Artificial silk is preliminarily mordanted with a 2% tannin solution, and after a considerable an hour at 50 C. with a solution of aluminium salt-containing emulsion of 15 g. per litre. This emulsion has the following composition:

30 parts of good quality gelatin are swollen in 550 parts of water and the glue is caused to melt by application of heat; by means of a stirring mechanism a mixture of 110 parts of paraffln (flow point t), 20 parts of bleached Montan wax and 80 parts of paraflin oil are stirred in. Whilst further stirringin the hot a solution of 80 parts of aluminium formate dissolved in 400 parts of water are slowly added, and thereupon the whole then cooled down. 1 v

The material is then rinsed in the cold and squeezed out and after drying dyed for three quarters of an hour at 60 C. in a bath of 1000 parts of water, 2 parts of rhodamine B (Schultz,

Farbstoiftabellen, volume 1, 7th edition, No. 864) and 5 parts of glacial acetic acid, after which it is rinsed. hot and cold. in the usual manner, squeezed out, dried and ironed. The water repolling efiect is very marked.

Example 4 Artificial sills is mordanted as in the above example, fixed, and then simultaneously dyed and blue (Schultz, Farbstofitabellen, 7th edition, volume 1, No. 1038).The bath has the following composition:

A solution of one gram of methylene blue R, 500 grams of water-(50 C.) and 5 g. of glacial acetic acid are filtered into an emulsion of g.

It is then fixed in a 0.1%

oi a substance according g. of water (50 0.). ducedat 50 0. and dyed for one hour at 60 C. solution of tartar emetic to Example 5 and 500 (the treatment being effected for half an hour at ordinary temperature) and thereupon rinsed and dried. The water-repelling action of the material treated in this way is very good.

l'larample 5.--Ncphtol dyeing Cotton'is bottomed or 30 minutes in a seat solutionaof sodium naphtholate AS SW (betahydroxynaphthoic acid; betanaphthallde) and Water j root Water-proofing emulsion made as described below dust red m base (d-chlor-o-toluidine dchults, Fnrbstofitabehen, 7th edition, volume 1, No. 82) dissolved-in glacial ace gm swirl I 1 After thorough stirring potassium nitrite dissolved in distilled water'is added"- 2 The emulsion referred to above is made as lolgenlzation is then is homogenized under pressure and len, 7th edition,

The material is then intro Parts with an aluminium formate solution which has been prepared by dissolving 1.55 leg. of 50% hydroxide of alumina in 1.75 kg. of 90% formic carried out at a pressure of 100 atmospheres. With the concentration emacld. Homoployed 50 kg. of a white paste are obtained after cooling.

Generation of the dye is carried'out for 30 minutes at 31 0.; the material is then twicerinsed, dried and ironed.

Drop value: 26 drops.

Example 6.-Indigo vat White raw wool fabric is boiled out and intro- The impregnating substance, together with the tartaric acid, is neutralized by means of ammonia. The fabric is dyed in the usual way and after hanging awhile is dried. The value for the imperviousness to water for a falling height of 20 cms. amounted to 12 drops. Operations are carried out in a similar manner with hydro'ne blue B (Schultz, Farbstofitabellen, 7th edition, volume 1, No. i113);

Example 7 Skelned wool is dyed in the known manner by means of eriochrome red (Schultz,'Farbstofitabelvolume 1, No. 745) and thereupon afterchromed with potassium chromate in acid emulsion, which is made as follows:- f 14 parts'of sodium oleate are stirred up with 15 parts of swollen bone glue and the whole di luted with water. This solution is then stirred into 500 parts of a solution of for-mate of alumina; having a specific gravity of 1.095.

This emulsion is homogenized at 60 atmospheres pressure with the aid of suitable machines by forcing through ducts. The foregoing-emulsion is diluted fourfold and represents the above emulsion in the condition for use, in which afterchroming is carried out. The skeined wool is satisfactorily water-repelling and can be worked 'up into water-proof? articles of apparel.

volume 1, No. 230) has been found to be sucha dyestufi. This dyestufi acts in acid solution as a tanning agent, precipitates the glue and breaks down the emulsion. In this case emulsions are used which are stabilized for example by means of starch, dextrln, or mucilage. lIowever, in any after-chroming bath which may be used as in I the 'aitenchroming bath of Example 7, gluecontaining emulsion may be used. Outstanding waterproofing efiects are. already produced when fractions of a gram of impregnating agent per litre are used. The in'ipregnationdescribed can be used in the known manner in all dyeing appliances or apparatus.

Eaample 8.Inda.nthrene "cat A cotton fabric is treated at 60 C. in a hyposulphite vat of the following composition:

15 g. of a substance 500 g. of water 2 g. of dyestufi (in danthrenegolden orange G double paste: Schultz, Farbstoiftabellen, 7th edition, volume 1, No.- 1245) 3 g. of hyposulphite (Na2SaO4) 10 g. of common salt 5 g. of an emulsion of the following composition 1.5 kg. of 50% aluminium hydroxide. 2.1 kg. of formic acid 375 kg. of water 2 kg. of tartaric acid 7 of concentrated ammonia 99 kg. of paramn kg. of an oil fatty acid 10 kg. of potash lye B.) 20 kg. ofalue The fabric is dyed for one hour at about C'., rinsed, soaped in a 0.5% soap solution containing 1% of the above emulsion, and rinsed once warm and twice cold Five cos. of an alumina solution of 7 B. are added per litre of the lastrinsing bath. For a falling height of 30 cm. the

waterproof value amounts to 21 drops.

What I claim is:-

1. A method of simultaneously and uniformly dyeing and waterproofing textile materials, comprising treating said materials in usual alkaline dyestufi bath containing. also a stable emulsion of substantially. colorless water-repellent substances and aluminium formate and a. substance selected from a group consisting of tartaric acid and tartrates, added for the purpose of converting the aluminium salt into a complex compound;

2. The method of claim 1, as modified in that the tartrate recited therein is tartaric acid.

RUDOLF KERN. 

